CN115925056A - Preparation of phosphorus-doped titanium protoxide/titanium foam electrode and method for treating heavy metal wastewater by using phosphorus-doped titanium protoxide/titanium foam electrode - Google Patents
Preparation of phosphorus-doped titanium protoxide/titanium foam electrode and method for treating heavy metal wastewater by using phosphorus-doped titanium protoxide/titanium foam electrode Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a preparation method of a phosphorus-doped titanium protoxide/titanium foam electrode and a method for treating heavy metal wastewater by using the phosphorus-doped titanium protoxide/titanium foam electrode. The preparation method comprises the following steps: cleaning a titanium suboxide/titanium foam electrode, putting the titanium suboxide/titanium foam electrode into a tubular furnace in which sodium hypophosphite and the titanium suboxide/titanium foam electrode are placed in sequence according to the flow direction of inert gas, introducing the inert gas, performing heat treatment at 300-350 ℃, wherein the inert gas firstly passes through the sodium hypophosphite and then passes through the titanium suboxide/titanium foam electrode in the heat treatment process and is discharged out of the tubular furnace; and finally, naturally cooling the tubular furnace to room temperature, and performing post-treatment to obtain the phosphorus-doped titanium protoxide/foam titanium electrode. After the titanium suboxide/foam titanium electrode is doped with phosphorus, the catalytic performance of the titanium suboxide/foam titanium electrode is obviously improved, and the titanium suboxide/foam titanium electrode has a certain application prospect in the aspect of electrochemical treatment of complex heavy metal wastewater, and has the advantages of environmental friendliness, no secondary pollution and the like.
Description
Technical Field
The invention belongs to the technical field of water pollution treatment in environmental protection, and particularly relates to a preparation method of a phosphorus-doped titanium protoxide/foamed titanium electrode and a method for treating heavy metal wastewater by using the phosphorus-doped titanium protoxide/foamed titanium electrode.
Background
With the development of economy, environmental pollution and treatment problems accompanying industrial manufacturing are also highlighted. It should be noted that, in these industrial waste waters, a considerable portion of heavy metal ions are present in a complex state, because organic complexing agents (such as ethylenediaminetetraacetic acid, citric acid) are often added to the reaction solution used in industrial production to stabilize the heavy metal ions. Compared with free heavy metal ions, the complex heavy metal ions have great removal difficulty due to high stability and mobility, and are difficult to effectively remove from wastewater by conventional methods such as adsorption, chemical precipitation or ion exchange. And once the complex heavy metal is discharged into natural water, serious harm can be caused to the ecological environment and health. How to efficiently treat the complex heavy metals in the industrial wastewater is the key point in the field of industrial wastewater treatment.
Among many methods for treating complex heavy metals, the advanced oxidation technology based on fenton is concerned, and the principle is that an oxidizing agent (a fenton reagent compounded by hydrogen peroxide and ferrous ions) is added into wastewater to destroy an organic complexing agent, so that heavy metal ions are dissociated into free states, and then the heavy metal ions in the wastewater are removed by using a conventional precipitation or adsorption method. The method has the characteristic of high treatment efficiency of the complex heavy metal, but the use of the oxidant is limited by the safety of chemical transportation and storage, and the method is not suitable for a plurality of production enterprises with small wastewater generation amount.
Compared with the Fenton advanced oxidation technology, the electrochemical advanced oxidation does not need to add chemical reagents in the treatment process, does not cause secondary pollution, and has the advantages of easy operation control, mild reaction conditions and the like. In the electrochemical treatment process, water molecules are oxidized on the surface of the anode to generate active oxygen species with strong oxidizing property, and the active oxygen species further oxidize pollutants, so that the degradation and removal of organic pollutants are realized. At present, the electrochemical advanced oxidation technology mainly focuses on organic pollutant wastewater and is applied to a certain extent, but research reports related to treatment of complex heavy metal wastewater are few, and the problems of low treatment efficiency of complex heavy metal, poor electrode stability and the like need to be solved in future technical application. The core of the electrochemical advanced oxidation technology is anode material, and the preparation of high-efficiency and stable anode is the focus of research at present. In recent years, titanium dioxide attracts attention as a novel anode material, which has excellent conductivity, corrosion resistance and high oxygen evolution overpotential, and can oxidize water at a proper voltage to generate active oxygen species mainly containing hydroxyl radicals, thereby oxidizing organic pollutants in wastewater. For example, CN105967281a discloses a titanium-based titanium dioxide electrode preparation method, which adopts plasma spraying to spray titanium dioxide powder on the surface of a titanium substrate, so as to obtain a titanium-based titanium dioxide coated electrode, which can be used for degrading organic matters in sewage to reduce COD. CN108911052A discloses a doped titanium protoxide electrode and a preparation method and application thereof, wherein metal salt and/or metal oxide is adopted as a doping agent, and platinum or ruthenium and other doped titanium protoxide is obtained by high-temperature heat treatment at 800-1300 ℃ and is used for electrocatalytic degradation of phenol-containing wastewater. Noble metal doping improves the performance of the titanium suboxide/titanium plate electrode, but also correspondingly increases the overall cost of the material.
Among various published proposals, titanium-based titanium dioxide electrodes have better mechanical impact resistance and potential for practical application, but the performance of the titanium-based titanium dioxide electrodes is still a certain gap from the practical requirement. Particularly, aiming at the treatment of complex heavy metal sewage, the development of a titanium-based titanium dioxide electrode with more excellent performance has important significance.
Disclosure of Invention
The invention provides a phosphorus-doped titanium protoxide/foam titanium electrode, a preparation method and an application thereof aiming at the defects of the prior art. The phosphorus-doped titanium protoxide/foam titanium electrode is prepared by doping phosphorus into the titanium protoxide coating through low-temperature heat treatment. After phosphorus doping, the activity of the titanium suboxide/foam titanium electrode is obviously improved, and the degradation performance of complex heavy metal is further improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a phosphorus-doped titanium protoxide/foamed titanium electrode, which comprises the following steps:
preparing a titanium suboxide/foam titanium electrode;
cleaning a titanium oxide/titanium foam electrode, putting the cleaned titanium oxide/titanium foam electrode into a tubular furnace in which sodium hypophosphite and the titanium oxide/titanium foam electrode are arranged in sequence according to the flow direction of inert gas, introducing the inert gas, and carrying out heat treatment at 300-350 ℃, wherein the inert gas firstly passes through the sodium hypophosphite and then passes through the titanium oxide/titanium foam electrode in the heat treatment process and is discharged out of the tubular furnace; and finally, naturally cooling the tubular furnace to room temperature, and performing post-treatment to obtain the phosphorus-doped titanium protoxide/foam titanium electrode.
According to the scheme, the preparation method of the titanium suboxide/foamed titanium electrode comprises the following steps: and loading a titanium suboxide coating on the surface of the foamed titanium electrode by a plasma spraying method.
According to the scheme, the aperture of the foamed titanium electrode is 30-100 microns.
According to the scheme, the thickness of the titanium suboxide coating is 10-40 microns.
According to the scheme, the titanium suboxide/foamed titanium electrode is cleaned by the following steps: and (3) putting the titanium suboxide/foam titanium electrode into ethanol, carrying out ultrasonic treatment for 10-30 minutes at room temperature, and then taking out and drying by using argon.
According to the above scheme, preferably, as the raw material of the phosphorus doping element, the loading amount of the sodium hypophosphite is calculated according to the area of the titanium oxide/titanium foam electrode, and the loading amount of the sodium hypophosphite corresponding to each square centimeter of the electrode is 0.03-0.2 g.
According to the scheme, the flow rate of the inert gas is 20-50 mL/min; the gas is high-purity argon.
According to the scheme, the heat treatment time is 1-3 h.
According to the scheme, the post-treatment comprises the following steps: ultrasonic cleaning in deionized water.
The invention provides a phosphorus-doped titanium protoxide/foamed titanium electrode, which comprises a foamed titanium substrate and titanium protoxide loaded on the foamed titanium substrate, wherein the titanium protoxide is doped with phosphorus and has the content of 0.5-1.5 wt%.
According to the scheme, phosphorus is uniformly distributed in the titanium suboxide layer, and phosphorus forms P-O stable chemical bonds in the titanium suboxide layer.
In a third aspect, the invention provides the use of a phosphorus doped titanium suboxide/titanium foam electrode as an anode for electrochemical treatment of complex heavy metals.
The invention provides the application of the phosphorus-doped titanium protoxide/titanium foam electrode in electrochemical treatment of industrial wastewater of complex metal.
According to the scheme, the conditions of the electrochemical treatment are constant current treatment and the current density is5～15mA/cm 2 。
The doping method is simple and convenient, and can be used for carrying out phosphorus doping modification on the titanium dioxide material at a lower reaction temperature. After the titanium suboxide/foam titanium electrode is doped with phosphorus, the catalytic performance of the titanium suboxide/foam titanium electrode is obviously improved, and the titanium suboxide/foam titanium electrode has a certain application prospect in the aspect of electrochemical treatment of complex heavy metal wastewater, and has the advantages of environmental friendliness, no secondary pollution and the like. The method solves the problem that the activity of the existing titanium protoxide/titanium foam electrode is low, and the phosphorus-doped titanium protoxide/titanium foam electrode is expected to be applied to the field of environmental pollution treatment. The invention has the following beneficial technical effects:
1. the invention realizes the non-metal doping of the titanium suboxide electrode catalyst by using a simple heat treatment method. After phosphorus doping, the oxidation activity of the titanium suboxide/foamed titanium electrode is obviously improved, and the electrode has good cyclic usability;
2. compared with other noble metal doping, the doping element phosphorus adopted in the invention has lower cost, and the phosphorus forms stable chemical bonds in the titanium suboxide, so that the doped electrode has better stability;
3. according to the invention, the capability of titanium protoxide anode material for generating hydroxyl free radicals is effectively enhanced by adopting phosphorus doping, so that the complex heavy metal ions in the wastewater are in a complex free state, and the treatment efficiency of the metal wastewater is improved;
4. the heat treatment adopted by the invention has low doping temperature, and can not damage the mechanical strength and the pore structure of the foam titanium matrix.
Drawings
FIG. 1 scanning electron microscope images of titanium suboxide/titanium foam (a) and phosphorus-doped titanium suboxide/titanium foam electrode (b) of the present invention
FIG. 2 is a graph showing the distribution of elements on the surface of a phosphorus-doped titanium suboxide/titanium foam of the present invention
FIG. 3 is an X-ray photoelectron spectrum of surface Ti 2P of titanium suboxide/titanium foam (TiSO/Ti-foam) and phosphorus-doped titanium suboxide/titanium foam (P-TiSO/Ti-foam) in accordance with the present invention
FIG. 4 is an X-ray photoelectron spectrum of surface P2P of phosphorus-doped titanium protoxide/titanium foam in the present invention
FIG. 5 is a comparison graph of the effect of removing Cr (III) -EDTA by breaking the complex of titanium suboxide/titanium foam (TiSO/Ti-foam) and phosphorus-doped titanium suboxide/titanium foam (P-TiSO/Ti-foam) electrodes in water according to the present invention, in which FIG. 5 (a) is a graph of the change of Cr (III) -EDTA concentration with the time of electrochemical treatment, and FIG. 5 (b) is a graph of the dynamic constant fit corresponding to the graph of (a)
FIG. 6 (a) is a graph showing the change of Cr (III) -EDTA concentration and total chromium concentration with time in the electrochemical removal of Cr (III) -EDTA from phosphorus-doped titanium suboxide/titanium foam according to the present invention, and FIG. 6 (b) is a graph showing the change of hexavalent chromium concentration in the solution during the treatment
FIG. 7 is a graph showing the degradation cycle stability of the phosphorous doped titanium monoxide electrode of the present invention.
Detailed Description
The following embodiments are provided to more clearly illustrate the technical means of the present invention, and are not intended to limit the present invention.
Example 1: preparation of phosphorus-doped titanium protoxide/foam titanium electrode
Firstly, loading a titanium suboxide coating on the surface of a foamed titanium electrode by a plasma spraying method, wherein the length and the width of the foamed titanium electrode are both 4 cm, the pore diameter is about 50 microns, and the thickness of the titanium suboxide coating obtained by plasma spraying is about 20 microns; then putting the titanium suboxide/foam titanium electrode into ethanol, carrying out ultrasonic treatment for 10 minutes at room temperature, and then taking out and drying by using argon; putting the cleaned titanium suboxide/titanium foam electrode into a quartz tube of a heat treatment tube furnace, simultaneously putting a crucible filled with 2 g of sodium hypophosphite into the quartz tube of the tube furnace, introducing 20mL/min of high-purity argon, and treating at 300 ℃ for 2h, wherein the argon firstly passes through the crucible filled with the sodium hypophosphite and then passes through the titanium suboxide/titanium foam electrode and is discharged out of the tube furnace in the heat treatment process; and finally, naturally cooling the tubular furnace to room temperature, taking out the treated electrode, and ultrasonically cleaning the electrode in deionized water to obtain the phosphorus-doped titanium protoxide/foamed titanium electrode.
As can be seen from the scanning electron microscope (figure 1) of the sample, the surface topography of the electrode after surface doping has not been changed significantly, and the element distribution diagram (figure 2) of the electrode after doping can be seenSo that the Ti, O and P on the surface of the electrode are uniformly distributed, which shows that the P element is uniformly distributed on the surface of the electrode. Subsequently, the titanium suboxide/titanium foam (TiSO/Ti-foam) and the phosphorus-doped titanium suboxide/titanium foam (P-TiSO/Ti-foam) were subjected to X-ray photoelectron spectroscopy test and peak-splitting fitting, and the result of high-resolution X-ray photoelectron spectroscopy analysis of Ti 2P is shown in FIG. 3, wherein a peak corresponding to P-O-Ti (459.9 eV) appears in the spectrum of the phosphorus-doped electrode compared with the undoped electrode, and Ti 3+ And Ti 4+ All the peaks in (a) are shifted, indicating that P is doped into the sub-titanium oxide layer on the surface. A P-O peak appears in a P2P high-resolution X-ray photoelectron spectroscopy analysis spectrogram (figure 4), and further illustrates that the prepared electrode successfully realizes phosphorus doping. The content of phosphorus in the titanium suboxide was 1.3wt% by EDS analysis.
Example 2: preparation of phosphorus-doped titanium protoxide/foam titanium electrode
Firstly, loading a titanium protoxide coating on the surface of a foamed titanium electrode by a plasma spraying method, wherein the length and the width of the foamed titanium electrode are both 4 cm, the pore diameter is about 30 micrometers, and the thickness of the titanium protoxide coating obtained by plasma spraying is about 15 micrometers; then putting the titanium suboxide/foam titanium electrode into ethanol, carrying out ultrasonic treatment for 10 minutes at room temperature, and then taking out and drying by using argon; putting the cleaned titanium suboxide/titanium foam electrode into a quartz tube of a heat treatment tube furnace, simultaneously putting a crucible filled with 1.5 g of sodium hypophosphite into the quartz tube of the tube furnace, introducing high-purity argon of 20mL/min, and treating at 330 ℃ for 2h, wherein the argon firstly passes through the crucible filled with the sodium hypophosphite in the heat treatment process, and then passes through the titanium suboxide/titanium foam electrode and is discharged out of the tube furnace; and finally, naturally cooling the tubular furnace to room temperature, taking out the treated electrode, and ultrasonically cleaning the electrode in deionized water to obtain the phosphorus-doped titanium protoxide/foam titanium electrode. By EDS analysis of an energy spectrometer, the content of phosphorus in the titanium dioxide is 0.9wt%.
Example 3: preparation of phosphorus-doped titanium protoxide/foam titanium electrode for electrochemical removal of complex chromium in water
50mL of 2.5mg/L Cr (III) -EDTA aqueous solution is used as simulated wastewater, and 50mmol/LNa is added into the simulated wastewater 2 SO 4 As electrolysisFurther, using the phosphorus-doped titanium protoxide/titanium foam electrode prepared in example 1 as an anode and a carbon felt as a cathode, a constant current was set to 100mA, and a reaction was performed for 3 hours, and the concentration of EDTA was measured using a high performance liquid chromatograph, the concentration of hexavalent chromium was measured using an ultraviolet spectrophotometer, and the total chromium concentration was measured using Inductively Coupled Plasma (ICP). Meanwhile, the undoped titanium protoxide/titanium foam electrode is used as the anode of the control experiment, and the Cr (III) -EDTA aqueous solution is electrochemically treated under the same conditions. The experimental results are shown in fig. 5, the phosphorus doped electrode can achieve 100% decomplexation and removal of Cr (iii) -EDTA within 3 hours, and the reaction rate constant is nearly 3 times that of the undoped electrode. Fig. 6 shows the change of the total chromium concentration and Cr (iii) -EDTA and the change of the concentration of hexavalent chromium in the solution during the electrochemical treatment, and it can be seen that the total chromium and Cr (iii) -EDTA are degraded synchronously, and there is no hexavalent chromium generated during the reaction, which indicates that trivalent chromium ions generated by breaking the complex during the reaction are rapidly deposited on the cathode, thereby avoiding the generation of hexavalent chromium with higher toxicity.
Example 4: stability of phosphorus-doped titanium protoxide/foam titanium electrode for electrochemical removal of complex chromium in water
50mL of 2.5mg/L Cr (III) -EDTA aqueous solution is used as simulated wastewater, and 50mmol/LNa is added into the simulated wastewater 2 SO 4 As an electrolyte, a phosphorus-doped titanium protoxide/titanium foam electrode prepared in example 1 was used as an anode, a carbon felt as a cathode, a current was set to 100mA, and the reaction was carried out for 3 hours, and a sample was taken at regular intervals and the change in EDTA concentration and the change in total chromium concentration were measured by a relevant instrument. When the Cr (III) -EDTA in the system is completely degraded, 50mL of Cr (III) -EDTA aqueous solution with the concentration of 2.5mg/L is added again, the degradation effect is continuously measured in the reaction process, and the step is completed once. The results are shown in fig. 7, and the phosphorus-doped titanium protoxide/titanium foam electrode still has good effect of removing Cr (III) -EDTA after 5 times of circulation, which indicates that the electrode has good stability.
Claims (10)
1. A preparation method of a phosphorus-doped titanium protoxide/foam titanium electrode is characterized by comprising the following steps: the method comprises the following steps:
preparing a titanium suboxide/foamed titanium electrode, wherein a titanium suboxide coating is loaded on the surface of the foamed titanium;
cleaning a titanium oxide/titanium foam electrode, putting the cleaned titanium oxide/titanium foam electrode into a tubular furnace in which sodium hypophosphite and the titanium oxide/titanium foam electrode are arranged in sequence according to the flow direction of inert gas, introducing the inert gas, and carrying out heat treatment at 300-350 ℃, wherein the inert gas firstly passes through the sodium hypophosphite and then passes through the titanium oxide/titanium foam electrode in the heat treatment process and is discharged out of the tubular furnace; and finally, naturally cooling the tubular furnace to room temperature, and performing post-treatment to obtain the phosphorus-doped titanium protoxide/foamed titanium electrode.
2. The method of claim 1, wherein: the preparation method of the titanium suboxide/foam titanium electrode comprises the following steps: loading a titanium protoxide coating on the surface of the foamed titanium electrode by a plasma spraying method; the aperture of the foamed titanium electrode is 30-100 micrometers; the thickness of the titanium suboxide coating is 10-40 microns.
3. The production method according to claim 1, characterized in that: the titanium suboxide/foam titanium electrode cleaning method comprises the following steps: putting the titanium suboxide/foam titanium electrode into ethanol, performing ultrasonic treatment for 10-30 minutes at room temperature, and then taking out and drying by using argon;
the flow rate of the inert gas is 20-50 mL/min; the gas is high-purity argon.
4. The method of claim 1, wherein: the loading capacity of the sodium hypophosphite is calculated according to the area of the titanium oxide/titanium foam electrode, and the loading capacity of the sodium hypophosphite corresponding to each square centimeter of the electrode is 0.03-0.2 g.
5. The production method according to claim 1, characterized in that: the heat treatment time is 1-3 h.
6. A phosphorus-doped titanium protoxide/foam titanium electrode material is characterized in that: comprises a foamed titanium substrate and titanium suboxide loaded on the foamed titanium substrate, wherein the titanium suboxide layer is doped with phosphorus and has the content of 0.5 to 1.5 weight percent.
7. The phosphorus-doped titanium protoxide/foam titanium electrode material of claim 6, wherein: phosphorus is uniformly distributed in the titanium suboxide layer, and phosphorus forms P-O stable chemical bonds in the titanium suboxide layer.
8. Use of the phosphorus doped titanium protoxide/foam electrode of claim 6 as an anode for electrochemical treatment of complex heavy metals.
9. Use of the phosphorus doped titanium protoxide/foam electrode of claim 6 in electrochemical treatment of industrial waste water of complex metals.
10. Use according to claim 9, characterized in that: the conditions of the electrochemical treatment are constant current and the current density is 5-15 mA/cm 2 。
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